Novel fluoroalkene-methyl acrylate copolymers by atom transfer radical polymerization

The first controlled atom transfer radical polymerization (ATRP) of methyl acrylate (MA) with fluoralkenes was demonstrated. The copolymerization rate and the extent of alkene incorporation are higher that those observed with simple 1-alkenes. The unique block terpolymer, poly[(MA-co-ethene)-b-(MA-co-nonafluorohexene)], was also synthesized by sequential addition of ethene and nonafluoro-1-hexene to an acrylate copolymerization system. The perfluorination of the pendant alkyl group increases monomer reactivity, as with styrene. The polymerization reaction kinetics of MA with three fluoroalkene comonomers F-hexene, F-octene, and F-decene were performed in anisole solution.